Surdfactant compositions containing salts of vinylsulfonanilides



7 3,116,257 Patented Dec. 31, 1963 This invention relates to a new classof surfactants characterized as metallic salts of vinylsulfonamides.More particularly this invention relates to the discovery thatvinylsulfonamides or sulfonanilides per so are not surface active, buttheir salts possess surface activity provided the organic portion of themolecule contains at least 8 carbon atoms.

In accordance with this invention 1 have discovered that the alkali andalkaline earth metal salts of vinylsulfonamides derived from olefinscontaining at least 8 carbon atoms have excellent surface-activeproperties. The vinylsulfonamides per se and the metallic salts ofvinylsul-fonamides derived from lower-molecular-weight olefins, i.e.,having from 2 to 7 carbon atoms, do not possess this surface activity.The surfactants of this invention may be represented by the formula:

wherein R, R R and R are hydrogen or hydrocarbon radicals containingfrom 1 to carbon atoms and may be of the same or differentconfiguration, i.e., alkyl, alkaryl, aryl, aralkyl, or cycloparafiinicradicals containing from 1 to 20 carbon atoms, the total number ofcarbon atoms in R, R and R is at least 6, or R contains at least 6carbon atoms or is an aryl group (e.g., phenyl), M is w alkali metal,i.e., sodium, potassium, lithium, rubidium, or cesium, or an alkalineearth metal, i.e., barium, calcium, strontium, and magnesium, and n isthe valence of M. The organic portion of the molecule comprises theolefinic carbon atoms along with R, R and R or the olefinic carbon atomsand R to constitute a total of at least 8 carbon atoms.

The process by which the above-defined vinylsulfonamides are preparedcomprises reacting about 1 mol of an olefin having at least 8 carbonatoms with about 2 mols of sulfur trioxide in complexed form, treatingthe reaction product with about 2 mols of a primary amine per mol ofolefin reactant, reacting the resulting product with a sufficientlystrong base to eliminate the amine and the sulfate group to form thevinylsulfonamide, and reacting the vinylsulfonamide with an oxide orhydroxide of an alkali or alkaline earth metal to form thesurface-active salt.

It becomes then a primary object of this invention to provide surfactmtsof the general formula supra.

Another object of the invention is to provide a process for preparingsurfactants of the general formula supra by the steps outlined above.

Another object of the invention is to provide'surfactants comprisingalkali metal salts of vinylsulfonamides wherein the organic portion ofthe molecule contains at least 8 carbon atoms.

Still another object of the invention is to provide surfactantscomprising alkaline earth metal salts of vinylsulfonamid'es wherein theorganic portion of the molecule contains at least 8 carbon atoms.

These and other objects and features of the invention will be describedor become apparent as the specification proceeds.

In order to demonstrate the invention, a number of non-limiting examplesare given:

Example 1 A 3.0-g. portion of the anilinium salt ofZ-hydrosulfato-1-dodecanesulfonanilide, previously prepared by reactingdodecene with diox-ane-sulfur trioxide complex and aniline, wasdissolved in 25 ml. of 1 N sodium hydroxide solution, and the resultingsolution was heated on a steam bath for 1 /2 hours. During this period,the viscosity of the clear solution increased appreciably. Then themixture was cooled in an ice bath and neutralized with 10% hydrochloricacid solution, yielding 1- dodecene-l-sulfonranilide having the formulaAfter the product had been filtered and recrystallized, it was in theform of white flakes which had a melting point of 55 57.5 C. The productwas soluble in hexane and warm oil, contained nitrogen and sulfur(qualitative elemental analysis), decolorized bromine solution in aceticacid, and consumed an equivalent of alkali when titrated, therebyindicating that it was as shown above. The infrared analysis was inaccord with the structure shown.

Example 2 Example 1 was repeated, using hexene to form 1-hexene-l-sulfon-an-ilide, having the formula (II) CH (CH CH=CHSO2NHExample 3 A 45-mg. portion of product (1) of Example 1 was treated with1.34 ml. of 0.1035 N potassium hydroxide solution to prepare thepotassium salt of l-dodecene-lsulfonanilide, having the formula, (III)[CH (CH CH= CHSO N [K] 69 The volume of the resulting mixture wasincreased to 50 ml. by adding distilled water, yielding a 0.1% aqueoussuspension of compound III.

Example 4 A 40.5-1ng. portion of product (-11) of Example 2 was treatedwith 1.63 ml. of 0.1035 N potassium hydroxide solution to prepare thepostassiurn salt of l-hexene-l-sulfonanilide, having the formula, 3( 2)3z H l The volume of the resulting mixture was increased to 50 ml. byadding distilled water, yielding a 0.1% aqueous solution of (IV).

Example 5 The procedure of Examples 3 and 4 were repeated, using sodiumhydroxide in place of potassium hydroxide, to obtain clear 0. 1% aqueoussolutions of the following products:

The 0.1% solutions of compounds (I), (ll), (Ill), (IV) were shaken 25times in a 250 ml. Erlenmeyer flask to determine the amounts of thefollowing results:

suds formed, with Suds Appearance of Rating Time to 5 Compound olutionat Room Suds Disap- Temperpearance ature l Turbid (insol.) 1g

1 2 hours. 10 9 1. 2 hours. 9 10 minutes.

atmg of 1 was assigned when the 250 ml. Erlenmeyer rating or 10 wasassigned When no suds formed. Thus, a rating of 3 indicates that 70% ofthe flask was filled with suds, a rating of 4 indicates that 60% of theflask Was filled, etc.

Example 6 is precipitated, namely, the anilinium salt of2-hydrosulfato-l-undecanesulfonanilide. The precipitate is filtered byuse of a vacuum and air-dried. The product is dissolved in excess of 1 Nsodium hydroxide solution and heated on a steam bath for 2 hours. Anincrease in viscosity of the solution occurs. The mixture is cooled onan ice bath and neutralized with 10% hydrochloric acid, yieldingl-undecane-l-sulfonanilide of the formula A 45-mg. portion of thisproduct is treated with 1.46 ml. of 0.1 N sodium hydroxide to preparethe sodium salt of l-undecene-l-sulfonanilide:

By following the foregoing examples, the various salts of this inventionmay be formed, such as:

Sodium salt of l-dodecene-l-sulfonanilide Potassium salt of1-dodecene-l-sulfonanilide Cesium salt of 1-dodecene-l-sulfonanilideLithium salt of l-dodecene-l-sulfonanilide Calcium salt ofl-dodecene-l-sulfonanilide Barium salt of l-dodecene-l-sulfonanilideStrontium salt of l-dodecene-l-sulfonanilide Sodium salt ofl-octene-l-sulfonanilide Potassium salt of l-octene-l-sulfonanilideCesium salt of l-octene-l-sulfonanilide Lithium salt ofl-octene-l-sulfonanilide Barium salt of l-octene-l-sulfonanilide Calciumsalt of 1-octene-'1-sulfonanilide Strontium salt ofl-octene-l-sulfonanilide Magnesium salt of l-octene-l-sulfonanilideSodium salt of l-nonene-l-sulfonanilide Potassium salt ofl-nonene-l-sulfonanilide Cesium salt of l-nonene-l-sulfonanilide Lithiumsalt of l-nonene-l-sulfonanilide Barium salt of l-nonene-l-sulfonanilideCalcium salt of l-nonene-l-sulfonanilide Strontium salt ofl-nonene-l-sulfonanilide Magnesium salt of l-nonene-l-sulfonanilideSodium salt of l-tridecene-l-sulfonanilide Cesium salt ofl-tridecene-l-sulfonanilide Lithium salt of l-tridecene-l-sulfonanilideBarium salt of l-tridecene-1-sulfonanilide Calcium salt ofl-tridecene-l-sulfonanilide Strontium salt ofl-tridecene-l-sulfonanilide Magnesium salt ofl-tridecene-l-sulfonanilide Sodium salt of l-tetradecene-l-sulfonanilidePotassium salt of 1-tetradecene-l-sulfonanilide Cesium salt ofl-tetradecene-l-sulfonanilide Lithium salt ofl-tetradecene-l-sulfonanilide Barium salt of1-tetradecene-l-sulfonanilide Calcium salt of1-tetradecene-l-sulfonanilide Strontium salt ofl-tetradecene-l-sulfonanilide Magnesium salt ofl-tetradecene-l-sulfonanilide Sodium salt ofl-pentadecene-l-sulfonanilide Potassium salt ofl-pentadecene-l-sulfonanilide Cesium salt ofl-pentadecene-l-sulfonanilide Lithium salt of1-pentadecene-l-sulfonanilide Barium salt ofl-pentadecene-l-sulfonanilide Calcium salt ofl-pentadecene-l-sulfonanilide Strontium salt ofl-pentadecene-l-sulfonanilide Magnesium salt of1-pentadecene-l-sulfonanilide Sodium salt of l-octene-1-N-methylsulfonamide Potassium salt of l-octene-l-N-ethyl sulfonamide Cesium saltof l-octene-l-N-propylsulfonamide Lithium salt of1-octene-l-N-isopropylsulfonamide Barium salt of1-octene-1-N-butylsulfonamide Calcium salt ofl-octene-l-N-t-butylsulfonamide Strontium salt ofl-octene-l-N-amylsulfonamide Magnesium salt of1-octene-l-N-amylsulfonamide Sodium salt of1-nonene-l-N-benzylsulfonamide Potassium salt of1-nonene-l-N-naphthylsulfonamide Cesium salt ofl-nonene-l-N-anthrylsulfonamide Lithium salt ofl-nonene-l-N-cyclohexylsulfonamide Barium salt ofl-nonene-l-N-cyclopentylsulfonamide Calcium salt of1-nonene-l-N-phenylethylsulfonamide Strontium salt ofl-nonene-l-N-phenylbutylsulfonamide Magnesium salt of1-nonene-I-N-phenylbutylsulfonamide Sodium salt ofl-dodecene-l-N-pentylsulfonamide Potassium salt ofl-undecene-l-N-eicosylsulfonamide Cesium salt ofl-undecene-l-N-nonadecy1sulfonamide Lithium salt of l-undecene-l-Noctadecylsulfonamide Barium salt of 1-undecene1-N-heptadecylsulfonamideCalcium salt of 1-undecene-1-N-dodecylsulfonamide Calcium salt ofl-undecene-l-N-anthrylsulfonamide Calcium salt ofI-undecene-1-N-benzohydrylsulfonamide Sodium salt of1-tetradecene-1-N-cyclobutylsulfonamide Potassium salt of1-tetradecene-l-N-durylsulfonamide Cesium salt of1-tetradecene-l-N-naphthylsulfonamide Lithium salt ofl-tetradecene-l-N-phenethylsulfonamide Barium salt of1-tetradecene-l-N-phenethylsulfonamide Calcium salt ofl-tetradecene-1-N-phenethyl-sulfonamide The olefinic starting materialfor the reaction of this invention may be any compound containing anolefinic double bond. The only limitation attaching to the olefiniccompound used is that there is no substituent groups present or attachedto R, R and R of the general formula which are reactable with the sulfurtrioxide complex used under the conditions of the reaction necessary tocause reaction at the double bond. The various sulfur trioxide complexesthat may be used in this reaction have differing reactivities and somerequire elevated tempera tures. Under some conditions, the intermediatesmay decompose faster than the hydrosulfate-compound can form, in whichevent lower yields result. Where R and R are hydrogen, saturated, alkylradicals, or cycloaliphatic radicals, no diificulty is experienced dueto sulfonation on the substituent group. Where R and R are aryl,alkaryl, heterocyclic, or other slightly reactive groups that maysulfonate across a double bond therein, the reaction of this inventionwill still take place but certain precautions are necessary to preventsulfonation of is these substituents. This is easily overcome by thechoice of sulfur trioxide complex and the reaction temperature orreaction time. The only disadvantage attaching to the use of startingmaterials having somewhat reactive substituent groups (R, R or R is thatlower temperatures may be necessary and the reaction time is extended.

Accordingly, the starting olefinic materials include the simple terminalolefins (R and R being hydrogen) such as octene-l, nonene-l, decene-l,undecene-l, dodecene-l, tridecene-l, tetradecene-l, pentadecene-l,hexadecene-l, heptadecene-l, octadecene-l, nonadecene-l, eicosene-l,heneicosene-l, docosene-l, tricosene-l, tetracosene-l, andpentacosene-1. Higher-molecular-weight terminal olefins, or mixturescontaining higher-molecular-weight terminal olefins from refinerystreams, alkylate streams, isomerization processes etc. may also beused.

Where R or R or both are alkyl groups, each may contain from 1 to carbonatoms including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl pentadecyl,hexadecyl, octadecyl, nonadecyl, and eicosyl as members of thestraight-chain alkyl series; or isopropyl, isobutyl, t-butyl, isohexyl,isooctyl, etc., as members of the branched-chain alkyl series. Suchinternal olefins as 2- methylnonene-l, 1,2-dimethyl octene-l,Z-ethyl-l-methylheptene-l, Z-methyl-l-ethyl heptene-l,2,2-diethyl-hexenel, Z-ethyl-l-propylpentene-l,2-propyl-t-ethylpentene-l, 1,2-dipropylbutene-l 1 ,Z-diisopropylbutenel1,2-dibutyl propylene, l-propyl-2-butyl propylene, 1,2-dimethylhexene-l,2-methyl-heptene-1, Z-ethyl-l-methylhexene-l, 1,2- di-t-butyl propylene,l-isopropyl-Z-isobutyl propylene, and the like are members containing atleast 8 carbon atoms. Higher-molecular-weight olefins constituting apreferred group are 1,2-diethyloctene-l, 1,2-dipropyloctene-1, 1,2-dibutyloctene-l 1,2-diisobutyloctene-l 1,2-di-t-butyloctene-l,1-butyl-2-propyl-nonene-1, l-hexyl-Z-heptyl-octene- 1,1-octyl-2-nonyl-octene-l, and 1-eicosyl-2-methyl-octene- 1.

Members of the group of olefinic starting materials containing othersubstituent groups, i.e., aryl, alkaryl, cycloparafiinic and aralkylradicals, include acenaphthenyl, anthryl, benzohydryl, benzyl,biphenylyl, bornyl, camphanyl, carbacryl, cuminyl, cumyl, cyclohexyl,cyclopropyl, cyclobutyl, cyclopentyl, cymyl, duryl, fenchanyl,fiuoroenl, indanyl, l-mesityl, 2-mesityl, phenanthryl, phenethyl, tolyl,and xylyl groups are phenylethylene, l,l-diphenylethylene,triphenylethylene, sym. diphenylethylene, diphenylethylethylene,diphenylbutylethylene, diphenylisopropylethylene,diphenylcyclohexylethylene,

phenylcyclopentylethylene, naphthyl dimethylethylene, 2-

butyl-S-phenyl pentene-l, 2,3-diphenyl pentene-l, 2- benzyl-octene-l,2,3-dinaphthyl pentene-l benzyl dimethylethylene, 3-furylpentene-l,4-anthryl-butene-1, dianthrylmethylene, 2-cyclohexyl-3-furylpentene-2.

The amine used in the reaction is selected from the group of primaryamines of the formula wherein R is a hydrocarbon radical having from 1to 20 carbon atoms and may be alkyl, aryl, alkaryl, aralkyl, orcycloparaffinic in structure. Species of amines include methylamine,ethylamine, propylamine, isopropylamine, butylamine, amyl orpentylamine, t-butylamine, isopentylamine, hexylamine, isohexylamine,heptylamine, octylamine, nonylamine, decylamine, dodecylamine,undecylamine, tridecylamine, tetradecylamine, pentadecylamine,hexadecylamine, eicosylamine, heptadecylamine, nonadecylamine as membersof the aliphatic series; cyclopropylamine, cyclobutvlamine,cyclopentylamine, cyclohexylamine, cycloheptylamine as members of thecycloparaffinic series; and benzylatnine, decahydronaphthylamine,aniline, laurylamine, oleylamine, eicosenylamine, furfurylarnine,4-ethoxycyclohexylamine, and the like.

Oxides and hydroxides of alkali metal and alkaline earth metals areused, preferably the hydroxides of alkali metals, to transformZ-hydrosulfato alkane'sulfonamides to the alkylene sulfonamide form andalso to form the final salts which constitute the surfactant compounds.

. For these purposes sodium hydroxide, potassium hydroxide, lithiumhydroxide, calcium oxide, calcium hydroxide, barium oxide, bariumhydroxide, barium hydroxide octahydrate, magnesium hydroxide,manganesium oxide, strontium oxide, and strontium hydroxide may be used.The base used to form the alkylene sulfonamide may be the same ordifferent base from that used to form the final salt. 1f the same baseis used, the salt can be isolated directly without acidification.

Any inorganic or strong organic acid may be used in the acidificationsteps. The inorganic acids include hydrochloric, hydrobromic,hydroiodic, hydrofluoric, sulfuric, nitric, carbonic, phosphoric, andsulfurous acids and the like. The organic acids include acetic,propionic, benzoic, lactic, citric, oxalic, butyri c, hydrocyanic,malonic, oleic, succinic, lauric, trichloroacetic, and valeric acids.Any acid capable of producing hydrogen ions may be used for these stepsof the reaction.

The reaction is carried out by merely bringing together the olefinicreactant with the sulfur trioxide complex at temperatures best suitedfor the particular complex employed. In general, sulfur trioxidecomplexes react at temperatures between -l0 to 120 C. A number of sulfurtrioxide complexes are available for the reaction. Dioxane-sulfurtrioxide, trimethylamine-sulfur trioxide, pyridine-sulfur trioxide,triethylamine-sulfur trioxide, dimethyl-formamide-sulfur trioxide,dioxane bis-sulfur trioxide, thioxane-sulfur trioxide, thioxanebis-sulfur trioxide and dimethylaniline-sulfur tr-ioxide complexes maybe used. There is a threshold temperature at which each complex becomesreactive. Consequently, the most suitable temperature range for thereaction will depend somewhat on the complexing agent used. The mostsuitable temperature range between -10 to 120 C. may be found by trialexperiments. In general, the reactivities of the complexes is known inthe art, and as in the case of pyridine-sulfur tnioxide, a temperaturebetween about to C. is suitable. It may be found that the intermediatesdecompose faster than they are formed, in which event lower temperaturesand longer contact times will be necessary.

The reaction time may be from five minutes to one day and no pressure isrequired. Since the complexes are solids, they are used in solution orslurry form with an inert solvent. Suitable solvents include ethylenedichloride, ethylene trichloride, various organic esters such as ethylacetate, butyl acetate, propyl acetate, unreactive naphthas or mineraloils, mineral spirits, VM&P naphtha, Stoddard solvent, and cyclohexane.With diox anesulfur trioxide as the reactant complexing agent, oneexpedient is to use an excess over the stipulated 1 molar quantitywhereby the excess acts as a solvent for the reaction. Other of thecomplexing agents may be used in this manner. Agitation is applied tothe reaction in a known manner or may be omitted, although its useshortens the reaction time.

A color change will be observed generally as an indication of thecompletion of the first stage of the reaction. Various other expedients,such as detection of unreacted olefin, or complex, may be used to followthe reaction and determine when equilibrium has been reached.

The addition of the reactant nitrogen compound in the second step of thereaction is conducted gradually with continued agitation. This stage ofthe reaction is easily followed since the beta-sulfato products aresolids and precipitate from the reaction mixture. Various known methodsof separating the solid product may be used. Filtration under vacuum isone expedient, and centrifuging or settling may be also used. Theproduct may be used per se without separation and recrystallization,although for most uses it is the better practice to separate and purifythe end products. The products may be recrystallized from any of thesolvents mentioned herein or water may be used for this purpose.Identification is made through melting points, mixed melting points,refractive index, infrared analyses or analyses for the elements. Thereaction may be conducted batchwise or on a continuous basis.

The steps of transforming the hydrosulfato-sulfonamide orhydrosulfatosulfonanilide compound to the alkylenel-sulfonamide orialkylene-l-sulfonanilide form is carried out using a solution of abase. Generally solutions of 0.1 to 2 N are sufficient, and aqueoussolutions are preferred, because emulsion difiiculties are avoided andproduct separation is facilitated. Either concentrated or dilute aqueoussolutions may be used. The temperature of this phase of the reaction isabout 50 (3.10 150 C. and preferably about 100 C. The cooling stepfollowing this base treatment is carried out at about -10 C. to 10 C. orthe temperature of an ice bath. The neutralization step following iscarried out at room temperature as is the step of forming the salt endproduct. Some application of heat, to the temperature of a steam bath,facilitates the final sa-lt formation.

As one feature of the invention wherein the neutralization step iseliminated by using a base of a metal which produces the desired saltdirectly, the resulting sulfate salt of the base can either be removedfrom the product or left therein as a builder for the sulfonate product.The sulfate salt of the base can be removed by filtering, centrifugingor other means applicable to the separation of inorganic salts fromorganic salts. Mixed salts of the vinylsulfonamides of this inventionare also contemplated wherein mixtures of bases of alkali and alkalineearth metals are used in either the neutralization step to form themixed vinylsulfonamide directly or in the final step, afterneutralization, wherein the amide product is reacted with a base salt ofthe metal M.

Since many apparently widely different embodiments of the invention maybe made without departing materially from the spirit and scope thereof,it is to be understood that the invention is not limited to the specificembodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A surfactant composition consisting essentially of an aqueoussolution of a salt of a vinylsulfonamide of the formula:

wherein R, R and R are substituents of the group consisting of hydrogen,alkyl of from 1 to 20 carbon atoms, phenyl, cyclopentyl, cyclohexyl,naphthyl, benzyl, furyl and anthryl, R is a substituent of the groupconsisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 7 carbonatoms, benzyl, decahydronaphthyl, phenyl, allyl, eicosenyl, furfuryl and4-ethoxycyclohexyl, the minimum total number of carbon atoms in thealkylene portion of the molecule being 8, M is a metal of the groupconsisting of sodium, potassium, lithium, rubidium, cesium, barium,calcium, strontium and magnesium and n is the valence of M.

2. A surfactant composition in accordance with claim 1 in which R is analkyl of from 1 to 20 carbon atoms, R and R are hydrogen, R is phenyland M is sodium.

3. A surfactant composition in accordance with claim 1 in which R is analkyl of from 1 to 20 carbon atoms, R and R are hydrogen, R is phenyland M is potassium.

4. A surfactant composition in accordance with claim 1 consistingessentially of about 1% by weight of said vinylsulfonamide salt. 7 A

5. A surfactant composition consisting essentially of the aqueousalkaline solution of the alkali metal salt ofl-dodecene-l-sulfonanilide.

6. A surfactant composition consisting essentially of the aqueousalkaline solution of the alkaline earth metal salt of1-dodecene-l-sulfonanilide.

7. A surfactant composition consisting essentially of the aqueoussolution of the sodium salt of l-dodecene-lsulfonanilide.

8. A surfactant composition consisting essentially of the aqueousalkaline solution of the potassium salt of l-dodecene-l-sulfonanilide.

9. A surfactant composition consisting essentially of the aqueousalkaline solution of the potassium salt of 1-undecene-l-sulfonanilide.

References Cited in the file of this patent UNITED STATES PATENTS2,948,753 Kranz Aug. 9, 1960 2,964,538 Kundiger et al. Dec. 13, 1960FOREIGN PATENTS 7 823,970 Germany Dec. 6, 1951 OTHER REFERENCES

1. A SURFACTANT COMPOSITION CONSISTING ESSENTIALLY OF AN AQUEOUSSOLUTION OF A SALT OF A VINYLSULFONAMIDE OF THE FORMULA:
 5. A SURFACTANTCOMPOSITION CONSISTING ESSENTIALLY OF THE AQUEOUS ALKALINE SOLUTION OFTHE ALKALI METAL SALT OF 1-DODECENE-1-SULFONANILIDE.